Fibre-reactive dyes, their preparation and their use

ABSTRACT

Reactive dyes of formula 
                         
wherein
         Q 1  and Q 2  are each independently of the other hydrogen or unsubstituted or substituted C 1 -C 4 alkyl,   D 1  is the radical of a diazo component, which is itself a mono- or dis-azo dye or contains such a dye,   D 2  has the same definition as D 1  or is a radical of formula       
                         
wherein
         (Q 3 ) 0-3  denotes from 0 to 3 identical or different substituents selected from the group halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy and sulfo and   Z 1  is a radical of formula
 
—SO 2 —Y   (3a),
 
—NH—CO—(CH 2 ) m —SO 2 —Y  (3b),
 
—CONH—(CH 2 ) n —SO 2 —Y  (3c),
 
—NH—CO—CH(Hal)-CH 2 -Hal  (3d) or
 
—NH—CO—C(Hal)=CH 2   (3e),
   Y is vinyl or a —CH 2 —CH 2 —U radical and U is a group that is removable under alkaline conditions,       m and n are each independently of the other the number 2, 3 or 4, and   Hal is halogen,
 
are suitable for dyeing cellulosic or amide-group-containing fibre materials.

The present invention relates to fibre-reactive dyes, to a process fortheir preparation and to their use in the dyeing or printing of textilefibre materials.

The practice of dyeing using reactive dyes has recently led to higherdemands being made on the quality of the dyeings and the economicefficiency of the dyeing process. As a result, there continues to be aneed for novel reactive dyes having improved properties, especially inrespect of their application.

Dyeing nowadays requires reactive dyes that have sufficientsubstantivity and at the same time have good ease of washing off ofunfixed dye. They should also have a good colour yield and highreactivity, the objective being to provide especially dyeings havinghigh degrees of fixing. The known dyes do not satisfy these requirementsin all properties.

The problem underlying the present invention is accordingly to find, forthe dyeing and printing of fibre materials, novel improved reactive dyeshaving the qualities characterised above to a high degree. The noveldyes should especially be distinguished by high fixing yields and highfibre-dye bond stabilities, and in addition it should be possible fordye not fixed to the fibre to be washed off readily. The dyes shouldalso yield dyeings having good allround fastness properties, for examplefastness to light and to wetting.

It has been found that the problem posed is largely solved by the noveldyes defined herein-below.

The present invention therefore relates to reactive dyes of formula

wherein

-   Q₁ and Q₂ are each independently of the other hydrogen or    unsubstituted or substituted C₁-C₄alkyl,-   D₁ is the radical of a diazo component, which is itself a mono- or    dis-azo dye or contains such a dye,-   D₂ has the same definition as D₁ or is a radical of formula

wherein

-   (Q₃)₀₋₃ denotes from 0 to 3 identical or different substituents    selected from the group halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxy    and sulfo and-   Z₁ is a radical of formula    —SO₂—Y   (3a),    —NH—CO—(CH₂)_(m)—SO₂—Y   (3b),    —CONH—(CH₂)_(n)—SO₂—Y   (3c),    —NH—CO—CH(Hal)-CH₂-Hal   (3d) or    —NH—CO—C(Hal)=CH₂   (3e),

Y is vinyl or a —CH₂—CH₂—U radical and U is a group that is removableunder alkaline conditions,

m and n are each independently of the other the number 2, 3 or 4, and

Hal is halogen,

with the proviso that the dye of formula (1) does not contain ahydroxysulfonylmethyl group.

As C₁-C₄alkyl there come into consideration for Q₁, Q₂ and Q₃, eachindependently of the others, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, especiallymethyl and ethyl. The alkyl radicals Q₁ and Q₂ may be unsubstituted ormay be substituted, for example, by hydroxy, sulfo, sulfato, cyano,carboxy, C₁-C₄alkoxy or by phenyl, preferably by hydroxy, sulfo,C₁-C₄alkoxy or by phenyl. The corresponding unsubstituted radicals arepreferred.

Preferably, one of the radicals Q₁ and Q₂ is hydrogen and the other ofthe radicals Q₁ and Q₂ is one of the above-mentioned unsubstituted orsubstituted C₁-C₄alkyl radicals.

Q₁ and Q₂ are especially preferably hydrogen.

As C₁-C₄alkoxy there come into consideration for Q₃, for example,methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy andtert-butoxy, preferably methoxy and ethoxy and especially methoxy.

As halogen there come into consideration for Q₃, for example, fluorine,chlorine, bromine and iodine, preferably chlorine and bromine andespecially chlorine.

Preferably, (Q₃)₀₋₃ denotes from 0 to 3 identical or differentsubstituents selected from the group C₁-C₄alkyl, C₁-C₄alkoxy and sulfo,especially methyl, methoxy and sulfo.

Hal is, for example, chlorine or bromine, especially bromine.

As leaving group U there come into consideration, for example, —Cl, —Br,—F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄alkyl and—OSO₂—N(C₁-C₄alkyl)₂. U is preferably a group of formula —Cl, —OSO₃H,—SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, especially —Cl or —OSO₃H andmore especially —OSO₃H.

Examples of suitable radicals Y are accordingly vinyl, β-bromo- orβ-chloro-ethyl, β-acetoxy-ethyl, β-benzoyloxyethyl, β-phosphatoethyl,β-sulfatoethyl and β-thiosulfatoethyl.

Preferably, Y is independently vinyl, β-chloroethyl or β-sulfatoethyl,especially vinyl or β-sulfatoethyl.

m and n are preferably each independently of the other the number 2 or3.

m is especially preferably the number 3.

n is especially preferably the number 2.

Preferably, Z₁ is a radical of formula (3a), (3b) or (3c), especially offormula (3a) or (3c) and more especially of formula (3a), the variableshaving the definitions and preferred meanings given hereinabove.

As substituents of the radical D₁ there come into consideration thesubstituents customary for azo dyes. The examples which follow may bementioned: C₁-C₄alkyl, which is understood to include methyl, ethyl, n-and iso-propyl and n-, iso-, sec- and tert-butyl; C₁-C₄alkoxy, which isunderstood to include methoxy, ethoxy, n- and iso-propoxy and n-, iso-,sec and tert-butoxy; hydroxy-C₁-C₄alkoxy; phenoxy; C₂-C₆alkanoylaminounsubstituted or substituted in the alkyl moiety by hydroxy or byC₁-C₄alkoxy, such as, for example, acetylamino, hydroxyacetyl-amino,methoxyacetylamino or propionylamino; benzoylamino unsubstituted orsubstituted in the phenyl moiety by hydroxy, sulfo, halogen, C₁-C₄alkylor by C₁-C₄alkoxy; C₁-C₆alkoxy-carbonylamino unsubstituted orsubstituted in the alkyl moiety by hydroxy, C₁-C₄alkyl or byC₁-C₄alkoxy; phenoxycarbonylamino unsubstituted or substituted in thephenyl moiety by hydroxy, C₁-C₄alkyl or by C₁-C₄alkoxy; amino;N—C₁-C₄alkyl- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted inthe alkyl moiety/moieties by hydroxy, C₁-C₄alkoxy, carboxy, cyano,halogen, sulfo, sulfato, phenyl or by sulfophenyl, such as, for example,methylamino, ethylamino, N,N-dimethylamino, N,N-diethylamino,β-cyanoethylamino, β-hydroxyethylamino, N,N-di-β-hydroxyethylamino,β-sulfoethylamino, γ-sulfo-n-propylamino, β-sulfato-ethylamino,N-ethyl-N-(3-sulfobenzyl)amino, N-(β-sulfoethyl)-N-benzylamino;cyclohexylamino; N-phenylamino or N—C₁-C₄alkyl-N-phenylaminounsubstituted or substituted in the phenyl moiety by nitro, C₁-C₄alkyl,C₁-C₄alkoxy, carboxy, halogen or by sulfo; C₁-C₄-alkoxycarbonyl, forexample methoxy- or ethoxy-carbonyl; trifluoromethyl; nitro; cyano;halogen, which is generally understood to include, for example,fluorine, bromine and especially chlorine; ureido; hydroxy; carboxy;sulfo; sulfomethyl; carbamoyl; carbamido; sulfamoyl; N-phenylsulfamoylor N—C₁-C₄alkyl-N-phenylsulfamoyl unsubstituted or substituted in thephenyl moiety by sulfo or by carboxy; methyl- or ethyl-sulfonyl; andC₁-C₄alkylsulfonylamino.

Fibre-reactive radicals are also suitable as substituents of the radicalD₁.

Fibre-reactive radicals, such as, for example, the above-mentionedradicals of formulae (3a) to (3e), are to be understood as being thosewhich are capable of reacting with the hydroxy groups of cellulose, withthe amino, carboxy, hydroxy and thiol groups in wool and silk or withthe amino groups and, possibly, with the carboxy groups of syntheticpolyamides, to form covalent chemical bonds. The fibre-reactive radicalsare generally bonded to the dye radical directly or by way of a bridgingmember. Suitable fibre-reactive radicals are, for example, those whichcontain at least one removable substituent at an aliphatic, aromatic orheterocyclic radical or in which the said radicals contain a radicalsuitable for reaction with the fibre material, for example a vinylradical.

A fibre-reactive radical present in D₁ corresponds, for example, to theabove formula (3a), (3b), (3c), (3d) or (3e) or to the formula

wherein

-   X₁ is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl,-   T₁ independently has the same definition as X₁, is a    non-fibre-reactive substituent or is a fibre-reactive radical of    formula

wherein

-   R₁, R_(1a) and R_(1b) are each independently of the others hydrogen    or C₁-C₄alkyl,-   R₂ is hydrogen, C₁-C₄alkyl unsubstituted or substituted by hydroxy,    sulfo, sulfato, carboxy or by cyano, or a radical

R₃ is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen,C₁-C₄alkoxycarbonyl, C₁-C₄-alkanoyloxy, carbamoyl or the group —SO₂—Y,

-   alk and alk₁ are each independently of the other linear or branched    C₁-C₆alkylene,-   arylene is a phenylene or naphthylene radical unsubstituted or    substituted by sulfo, carboxy, C₁-C₄alkyl, C₁-C₄alkoxy or by    halogen,-   Q is an —O— or —NR₁— radical wherein R₁ is as defined above,-   W is a —SO₂—NR₂—, —CONR₂— or —NR₂CO— group, wherein R₂ is as defined    above,-   Y has the definition and preferred meanings given hereinabove,-   Y₁ is a —CH(Hal)-CH₂-Hal or —C(Hal)=CH₂ group and Hal has the    definition and preferred meanings given hereinabove,-   k is the number 0 or 1,-   X₂ is halogen or C₁-C₄alkylsulfonyl,-   X₃ is halogen or C₁-C₄alkyl and-   T₂ is hydrogen, cyano or halogen.

R₁, R_(1a) and R_(1b) are each independently of the others preferablyhydrogen, methyl or ethyl and especially hydrogen.

R₂ is preferably hydrogen or C₁-C₄alkyl, such as, for example, methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl andespecially hydrogen, methyl or ethyl. Especially preferably, R₂ ishydrogen.

R₃ is preferably hydrogen.

When T₁ is a non-fibre-reactive substituent it may be, for example,hydroxy; C₁-C₄alkoxy; C₁-C₄alkylthio unsubstituted or substituted, forexample, by hydroxy, carboxy or by sulfo; amino; amino mono- ordi-substituted by C₁-C₈alkyl, wherein the alkyl may itself besubstituted, for example, by sulfo, sulfato, hydroxy, carboxy or byphenyl, especially by sulfo or by hydroxy, and may be interrupted one ormore times by the radical —O—; cyclohexylamino; morpholino;N—C₁-C₄alkyl-N-phenylamino, phenylamino or naphthylamino, wherein thephenyl or naphthyl is unsubstituted or substituted, for example, byC₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, carboxy, sulfo or byhalogen and the alkyl is unsubstituted or substituted, for example, byhydroxy, sulfo or by sulfato.

Examples of suitable non-fibre-reactive substituents T₁ are amino,methylamino, ethylamino, β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino,morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or4-sulfophenylamino, 2,5-disulfophenylamino, 2-, 3- or4-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino,4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino,N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.

As a non-fibre-reactive substituent, T₁ is preferably C₁-C₄alkoxy;C₁-C₄alkylthio unsubstituted or substituted by hydroxy, carboxy or bysulfo; hydroxy; amino; N-mono- or N,N-di-C₁-C₄-alkylamino unsubstitutedor substituted in the alkyl moiety/moieties by hydroxy, sulfato or bysulfo; morpholino; phenylamino unsubstituted or substituted on thephenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or bymethoxy; or N—C₁-C₄alkyl-N-phenylamino unsubstituted or substituted onthe phenyl ring in the same way as phenylamino and in which the alkyl isunsubstituted or substituted by hydroxy, sulfo or by sulfato; ornaphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups.

Especially preferred non-fibre-reactive substituents T₁ are amino,N-methylamino, N-ethylamino, N-β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, morpholino, 2-, 3- or4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino,2,5-disulfophenylamino and N—C₁-C₄-alkyl-N-phenylamino.

X₁ is preferably halogen, for example fluorine, chlorine or bromine andespecially preferably chlorine or fluorine.

T₂, X₂ and X₃ as halogen are, for example, fluorine, chlorine orbromine, especially chlorine or fluorine.

X₂ as C₁-C₄alkylsulfonyl is, for example, ethylsulfonyl ormethylsulfonyl and especially methylsulfonyl.

X₃ as C₁-C₄alkyl is, for example, methyl, ethyl, n- or iso-propyl or n-,iso- or tert-butyl and especially methyl.

X₂ and X₃ are preferably each independently of the other chlorine orfluorine.

T₂ is preferably cyano or chlorine.

alk and alk₁ are each independently of the other, for example, amethylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or1,6-hexylene radical or a branched isomer thereof.

Preferably, alk and alk₁ are each independently of the other aC₁-C₄alkylene radical and especially preferably an ethylene radical orpropylene radical.

arylene is preferably an unsubstituted or, for example, sulfo-, methyl-,methoxy- or carboxy-substituted 1,3- or 1,4-phenylene radical, andespecially preferably an unsubstituted 1,3- or 1,4-phenylene radical.

Q is preferably —NH— or —O— and especially preferably —O—.

W is preferably a group of formula —CONH— or —NHCO—, especially a groupof formula —CONH—.

k is preferably the number 0.

The reactive radicals of formulae (4a) to (4f) are preferably suchradicals in which W is a group of formula —CONH—, R₁ is hydrogen, methylor ethyl, R₂ and R₃ are each hydrogen, Q is the radical —O— or —NH—, alkand alk₁ are each independently of the other ethylene or propylene,arylene is phenylene unsubstituted or substituted by methyl, methoxy,carboxy or by sulfo, Y is vinyl or β-sulfatoethyl, Y₁ is —CHBr—CH₂Br or—CBr═CH₂ and k is the number 0.

A fibre-reactive radical present in D₁ preferably corresponds to aradical of the above formula (3a), (3b), (3c), (3d), (3e) or (3f),wherein Y is vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromine,R_(1a) is hydrogen, m and n are each independently of the other thenumber 2 or 3, X₁ is halogen, T₁ is C₁-C₄alkoxy; C₁-C₄alkylthio;hydroxy; amino; N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted in the alkyl moiety/moieties by hydroxy, sulfato or bysulfo; morpholino; phenylamino or N—C₁-C₄alkyl-N-phenylaminounsubstituted or substituted on the phenyl ring by sulfo, carboxy,acetylamino, chlorine, methyl or by methoxy, and in which the alkyl isunsubstituted or substituted by hydroxy, sulfo or by sulfato; ornaphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups,or T₁ is a fibre-reactive radical of formula—NH—(CH₂)₂₋₃—SO₂—Y   (4a′),—NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃—SO₂—Y   (4b′),

especially (4c′) or (4d′), wherein

-   (R₄)₀₋₂ denotes from 0 to 2 identical or different substituents from    the group halogen, C₁-C₄-alkyl, C₁-C₄alkoxy and sulfo, preferably    from the group C₁-C₄alkyl, C₁-C₄alkoxy and sulfo and especially from    the group methyl, methoxy and sulfo,-   Y has the definition and preferred meanings given hereinabove, and-   Y₁ is a —CH(Br)—CH₂—Br or —C(Br)═CH₂ group.

In the case of the radicals of formulae (4a′) and (4b′), Y is preferablyβ-chloroethyl. In the case of the radicals of formulae (4c′) and (4d′),Y is preferably vinyl or β-sulfatoethyl.

A preferred embodiment of the present invention relates to dyes whereinD₁ corresponds to a radical of formula

wherein

-   R₅ has the definition and preferred meanings given hereinabove for    R₁, R_(1a) and R_(1b),-   X₄ has the definition and preferred meanings given hereinabove for    X₁, and is especially chlorine, and-   T₃ is a monoazo- or disazo-amino radical of formula    D₃-N═N-(M-N═N)_(u)—K₁—NR₆—  (6) or    —NR₆-D₃-N═N-(M-N═N)_(u)—K₁   (7),    wherein-   D₃ is the radical of a diazo component, of the benzene or    naphthalene series, M is the radical of a middle component, of the    benzene or naphthalene series, K₁ is the radical of a coupling    component, of the benzene, naphthalene, pyrazolone,    6-hydroxypyridone-(2) or acetoacetic acid arylamide series, R₆ has    the definition and preferred meanings given hereinabove for R₁,    R_(1a) and R_(1b), and u is the number 0 or 1, wherein D₃, M and K₁    may carry substituents customary for azo dyes.

The expression “substituents customary for azo dyes” is understood toinclude both fibre-reactive and non-fibre-reactive substituents, suchas, for example, the substituents indicated above for D₁.

As non-fibre-reactive substituents for D₃, M and K₁ in T₃ there comeinto consideration preferably C₁-C₄alkyl or C₁-C₄alkoxy each of whichmay themselves be substituted by hydroxy, C₁-C₄alkoxy, sulfo or bysulfato; halogen; carboxy; sulfo; nitro; cyano; trifluoromethyl;sulfamoyl; carbamoyl; amino; ureido; hydroxy; sulfomethyl;C₂-C₄alkanoylamino; C₁-C₄alkylsulfonylamino; benzoylamino unsubstitutedor substituted on the phenyl ring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen orby sulfo; and phenyl unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy or by sulfo.

The monoazo- or disazo-amino radicals of formula (6) or (7) containpreferably at least one sulfo group.

Preferred monoazo- and disazo-amino radicals T₃ are the radicals offormulae

wherein (R₇)₀₋₃ denotes from 0 to 3 identical or different substituentsfrom the group C₁-C₄-alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, halogen,carboxy and sulfo,

-   (R₈)₀₋₃ denotes from 0 to 3 identical or different substituents from    the group halogen, nitro, cyano, trifluoromethyl, sulfamoyl,    carbamoyl, C₁-C₄alkyl; C₁-C₄alkoxy unsubstituted or substituted by    hydroxy, sulfato or by C₁-C₄alkoxy; amino, C₂-C₄alkanoylamino,    ureido, hydroxy, carboxy, sulfomethyl, C₁-C₄alkylsulfonylamino and    sulfo, preferably from the group halogen, C₁-C₄alkyl; C₁-C₄alkoxy    unsubstituted or substituted by hydroxy, sulfato or by C₁-C₄alkoxy;    amino, C₁-C₄alkanoylamino, ureido and sulfo, and-   Z₂ is a radical of formula (3a), (3b), (3c), (3d), (3e) or (3f),    preferably (3a), (3b), (3c), 3d) or (3e) and especially (3a), the    mentioned fibre-reactive radicals having the definitions and    preferred meanings given hereinabove,

wherein R₉ is benzoylamino, C₂-C₄alkanoylamino, for example acetylaminoor propionylamino, or a radical of the above formula (3f), preferablyC₂-C₄alkanoylamino or benzoylamino, R_(1a), T₁ and X₁ in the radical offormula (3f) each having the definitions and preferred meanings givenhereinabove,

wherein (R₁₀)₀₋₃ denotes from 0 to 3 identical or different substituentsfrom the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo,

wherein R₁₁ and R₁₃ are each independently of the other hydrogen,C₁-C₄alkyl or phenyl, and R₁₂ is hydrogen, cyano, carbamoyl orsulfomethyl,

wherein

-   (R₇)₀₋₃, (R₈)₀₋₃ and (R₁₀)₀₋₃ each have the definitions and    preferred meanings given hereinabove,-   (R₁₄)₀₋₃ and (R₁₅)₀₋₃, each independently of the other, denotes from    0 to 3 identical or different substituents from the group    C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo, and Z₂ has the    definition and preferred meanings given hereinabove.

The numbers at the naphthyl rings of the radicals of formulae (8a),(8b), (8c), (8d), (8e), (8g) and (8h) indicate the preferred bondingpositions.

The radicals (R₇)₀₋₃ in the disazoamino radicals of formulae (8n) and(8p) preferably denote from 0 to 3 sulfo groups.

In an embodiment of interest, Z₂ in the radicals of formulae (8a), (8b),(8c), (8d), (8e), (8f), (8l), (8m), (8n), (8o) and (8p) is hydrogen.

Especially preferred monoazo- and disazo-amino radicals T₃ are theradicals of formulae (8a), (8b), (8d), (8e), (8f), (8k) and (8m),especially (8b), (8e), (8k) and (8m).

In a further preferred embodiment of the present invention, D₁ is aradical of formula-D₄-N═N—K₂   (9) orD₄-N═N—K₃—  (10),preferably of formula (10), wherein D₄ is the radical of a diazocomponent, of the benzene or naphthalene series, K₂ is the radical of acoupling component, of the benzene, naphthalene, pyrazolone,6-hydroxypyridone-(2) or acetoacetic acid arylamide series and K₃ is theradical of a coupling component, of the benzene or naphthalene series,wherein D₄, K₂ and K₃ may carry substituents customary for azo dyes.

The expression “substituents customary for azo dyes” is understood toinclude both fibre-reactive and non-fibre-reactive substituents, suchas, for example, the substituents indicated above for D₁.

As non-fibre-reactive substituents for D₄, K₂ aund K₃ there come intoconsideration preferably C₁-C₄alkyl or C₁-C₄alkoxy each of which maythemselves be substituted by hydroxy, C₁-C₄-alkoxy, sulfo or by sulfato;halogen; carboxy; sulfo; nitro; cyano; trifluoromethyl; sulfamoyl;carbamoyl; amino; ureido; hydroxy; sulfomethyl; C₂-C₄alkanoylamino;C₁-C₄alkylsulfonylamino; benzoylamino unsubstituted or substituted onthe phenyl ring by C₁-C₄alkyl, C₁-C₄-alkoxy, halogen or by sulfo; andphenyl unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄-alkoxy,halogen, carboxy or by sulfo.

As fibre-reactive substituents for D₄, K₂ and K₃ there come intoconsideration preferably the radicals of formulae (3a), (3b), (3c),(3d), (3e) and (3f), especially (3a) and (3f) and more especially (3a),the said radicals having the definitions and preferred meanings givenhereinabove. In an embodiment of interest, a radical of formula (3a) ispreferred as fibre-reactive substituent for D₄ and a radical of formula(3f) is preferred as fibre-reactive substituent for K₃.

Monoazo radicals of formula (9) or (10) contain preferably at least onesulfo group.

Preferred monoazo radicals D₁ of formula (10) correspond to the radicalsof formulae

wherein (R₇)₀₋₃ denotes from 0 to 3 identical or different substituentsfrom the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo andZ₂ is a fibre-reactive radical of formula (3a), (3c), (3d), (3e), (3f)or (3g), preferably (3a), (3c), (3d) or (3e) and especially (3a),wherein the said fibre-reactive radicals have the definitions andpreferred meanings given hereinabove,

wherein (R₇)₀₋₃ is as defined hereinabove, (R′₈)₀₋₃ denotes from 0 to 3identical or different substituents from the group halogen, nitro,cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁-C₄alkyl; C₁-C₄alkoxyunsubstituted or substituted by hydroxy, sulfato or by C₁-C₄alkoxy;amino, C₂-C₄alkanoylamino, ureido, hydroxy, carboxy, sulfomethyl,C₁-C₄alkylsulfonylamino, sulfo and a fibre-reactive radical of formula(3f), preferably from the group C₁-C₄alkyl; C₁₋₄alkoxy unsubstituted orsubstituted by hydroxy, sulfato or by C₁-C₄alkoxy; amino,C₂-C₄alkanoylamino, ureido, sulfo and a fibre-reactive radical offormula (3f), wherein R_(1a), T₁ and X₁ in the radical of formula (3f)have the definitions and preferred meanings given hereinabove, (R₁₅)₀₋₃denotes from 0 to 3 identical or different substituents from the groupC₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo and is preferablysulfo, and Z₂ has the definition and preferred meanings givenhereinabove.

The numbers at the naphthyl rings of the radicals of formulae (10a),(10b), (10e) and (10f) indicate the preferred bonding positions.

When R′₈ is a radical of formula (3f), then especially R_(1a) ishydrogen,

-   T₁ is amino; N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or    substituted in the alkyl moiety/moieties by hydroxy, sulfato or by    sulfo; morpholino; phenylamino unsubstituted or substituted on the    phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or by    methoxy; or N—C₁-C₄alkyl-N-phenylamino unsubstituted or substituted    on the phenyl ring in the same way as phenylamino and in which alkyl    is unsubstituted or substituted by hydroxy, sulfo or by sulfato; or    naphthylamino unsubstituted or substituted by from 1 to 3 sulfo    groups, and-   X₁ is chlorine.

As a radical of formula (10), D₁ is especially preferably a radical offormula (10i), (10j), (10k) or (10l), especially of formula (10j) or(10l).

Preferably, the radical D₁ corresponds to a radical of formula (5) or(11)

wherein

-   R₅ is hydrogen or C₁-C₄alkyl, preferably hydrogen, methyl or ethyl    and especially hydrogen,-   (R₇)₀₋₃ denotes from 0 to 3 identical or different substituents    selected from the group halogen,-   C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, carboxy and sulfo,    preferably from the group C₁-C₄alkyl, C₁-C₄alkoxy,    C₂-C₄alkanoylamino and sulfo,-   X₄ is fluorine or chlorine, preferably chlorine,-   T₃ is a radical of the above formula (8a), (8b), (8d), (8e), (8f),    (8k) or (8m), preferably (8b), (8e), (8k) or (8m), wherein the    variables have the definitions and preferred meanings given    hereinabove,-   Z₂ is a fibre-reactive radical of the above formula (3a), (3c),    (3d), (3e), (3f) or (3g), preferably (3a), (3c), (3d) or (3e) and    especially (3a), wherein the variables have the definitions and    preferred meanings given hereinabove, and-   K₃ is the radical of a coupling component of formula

wherein

-   R′₈ is hydrogen, sulfo, or C₁-C₄alkoxy unsubstituted or substituted    in the alkyl moiety by hydroxy or by sulfato, and-   R′_(8a) is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, C2-C₄alkanoylamino,    ureido or a radical of the above formula (3f), preferably hydrogen,    C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino or ureido, wherein    R_(1a), T₁ and X₁ in the radical of forromula (3f) have the    definitions and preferred meanings given hereinabove, and,    especially,-   R_(1a) is hydrogen,-   T₁ is amino; N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or    substituted in the alkyl moiety/moieties by hydroxy, sulfato or by    sulfo; morpholino; phenylamino unsubstituted or substituted on the    phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or by    methoxy; or N—C₁-C₄alkyl-N-phenylamino unsubstituted or substituted    on the phenyl ring in the same way as phenylamino and in which the    alkyl is unsubstituted or substituted by hydroxy, sulfo or by    sulfato; or naphthylamino unsubstituted or substituted by from 1 to    3 sulfo groups, and X₁ is chlorine.

There come into consideration as C₁-C₄alkyl for R₇ and R′_(8a), eachindependently of the other, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferablymethyl and ethyl and especially methyl.

There come into consideration as C₁-C₄alkoxy for R₇, R′₈ and R′_(8a),each independently of the others, for example, methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy and isobutoxy, preferably methoxy andethoxy. R₇ and R′_(8a) are especially methoxy. R′₈ is unsubstituted ormay be substituted in the alkyl moiety by hydroxy or by sulfato.

There come into consideration as halogen for R₇, each independently ofany other(s), for example, fluorine, chlorine and bromine, preferablychlorine and bromine and especially chlorine.

There come into consideration as C₂-C₄alkanoylamino for R₇ and R′_(8a),for example, acetylamino and propionylamino, especially acetylamino.

There comes into consideration as a radical of formula (3f) for R′_(8a)preferably a radical

wherein

-   R_(1a), is hydrogen,-   T₁ is amino; N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or    substituted in the alkyl moiety/moieties by hydroxy, sulfato or by    sulfo; morpholino; phenylamino or N—C₁-C₄alkyl-N-phenylamino    unsubstituted or substituted on the phenyl ring by sulfo, carboxy,    acetylamino, chlorine, methyl or by methoxy and in which the alkyl    is unsubstituted or substituted by hydroxy, sulfo or by sulfato; or    naphthylamino unsubstituted or substituted by from 1 to 3 sulfo    groups, and-   X₁ is fluorine or chlorine, preferably chlorine.

In an embodiment of interest, D₂ corresponds to a radical of formula(2), wherein (Q₃)₀₋₃ and Z₁ each have the definitions and preferredmeanings given hereinabove.

Preferably, the radical D₂ corresponds to a radical of formula

wherein

-   (R₃)₀₋₂ denotes from 0 to 2 identical or different substituents    selected from the group halogen,-   C₁-C₄alkyl, C₁-C₄alkoxy and sulfo, preferably from the group methyl,    methoxy and sulfo,-   Y₁ is a —CH(Br)—CH₂—Br or —C(Br)═CH₂ group,-   Y is vinyl or β-sulfatoethyl,-   m is the number 2 or 3, preferably 2, and-   n is the number 2 or 3, preferably 3.

Especially preferably, D₂ is a radical of the above formula (2a), (2b)or (2d), especially (2a); in an embodiment of interest the radical offormula (2a) is a radical of formula

wherein

-   Y is vinyl or β-sulfatoethyl, and    the numbers given in the formula indicate the possible bonding    positions of —SO₂—Y, the 4-position being preferred.

A preferred embodiment of the present invention relates to reactive dyesof formula (1)

wherein

-   Q₁ and Q₂ are hydrogen,-   D₁ corresponds to a radical of the above formula (5) or (11) wherein-   R₅ is hydrogen or C₁-C₄alkyl, preferably hydrogen, methyl or ethyl    and especially hydrogen,-   (R₇)₀₋₃ denotes from 0 to 3 identical or different substituents    selected from the group halogen,-   C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, carboxy and sulfo,    preferably from the group C₁-C₄alkyl, C₁-C₄alkoxy,    C₂-C₄alkanoylamino and sulfo,-   X₄ is fluorine or chlorine, preferably chlorine,-   T₃ is a radical of the above formula (8a), (8b), (8d), (8e), (8f),    (8k) or (8m), preferably (8b), (8e), (8k) or (8m), wherein the    variables have the definitions and preferred meanings given    hereinabove,-   Z₂ is a fibre-reactive radical of the above formula (3a), (3c),    (3d), (3e), (3f) or (3g), preferably (3a), (3c), (3d) or (3e) and    especially (3a), wherein the variables have the definitions and    preferred meanings given hereinabove, and-   K₃ is the radical of a coupling component of the above formula (12a)    or (12b) wherein-   R′₈ is hydrogen, sulfo, or C₁-C₄alkoxy unsubstituted or substituted    in the alkyl moiety by hydroxy or by sulfato, and-   R′_(8a) is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, C2-C₄alkanoylamino,    ureido or a radical of the above formula (3f), wherein R_(1a), T₁    and X₁ in the radical of formula (3f) have the definitions and    preferred meanings given hereinabove, and-   D₂ is a radical of the above formula (2aa) wherein-   Y is vinyl or β-sulfatoethyl, and    the numbers given in formula (2aa) indicate the possible bonding    positions of —SO₂—Y, the 4-position being preferred.

The present invention relates also to a process for the preparation ofdyes of formula (1) which comprises

(i) diazotisation of approximately one molar equivalent of an amine offormulaD₂-NH₂   (13)in customary manner and reaction with approximately one molar equivalentof a compound of formula

to form a compound of formula

and

(ii) diazotisation of approximately one molar equivalent of an amine offormulaD₁-NH₂   (16)in customary manner and reaction with approximately one molar equivalentof the compound of formula (15a) obtained according to (i) to form acompound of formula (1) wherein D₁, D₂, Q₁ and Q₂ each have thedefinitions and preferred meanings given hereinabove.

The diazotisation of the amines of formulae (13) and (16) is carried outin a manner known per se, for example using a nitrite, for example analkali metal nitrite such as sodium nitrite, in a mineral acid medium,for example in a hydrochloric acid medium, at temperatures of, forexample, from −5 to 40° C. and preferably at from 0 to 20° C.

The coupling to the coupling components of formulae (14) and (15a) iscarried out in a manner known per se at acidic or neutral to slightlyalkaline pH values, for example a pH value of from 0 to 8, and attemperatures of, for example, from −5 to 40° C., preferably from 0 to30° C.

The first coupling—(i)—takes place in an acidic medium, for example at apH of from 0 to 4, and the second coupling—(ii)—at elevated pH values,in a slightly acidic, neutral or slightly alkaline medium, for example apH value of from 4 to 8.

By proceeding as described hereinabove but, instead of usingapproximately one molar equivalent each of the amines of formulae (13)and (16) in process steps (i) and (ii), using in each case approximatelyone molar equivalent of a mixture of at least two, preferably two,non-identical amines, for example a 1:1 molar mixture of the compoundsof formulae (13) and (16), there is obtained first of all, according to(i), a mixture of compounds of formulae

and, on further reaction of the mixture of compounds of formulae (15a)and (15b) according to (ii), a mixture of dyes of formulae (1a), (1b),(1c) and (1d)

The present invention accordingly relates also to dye mixtures thatcomprise at least one dye of formulae (1a) and (1b) together with atleast one dye of formulae (1c) and (1d), especially one dye each offormulae (1a), (1b), (1c) and (1d), wherein D₁, D₂, Q₁ and Q₂ each havethe definitions and preferred meanings given hereinabove and D₁ and D₂are not identical.

The ratio of the dyes of formulae (1a), (1b), (1c) and (1d) in themixture can vary within wide limits and depends on the ratio of theparticular amines D₁-NH₂ and D₂-NH₂ used according to (i) and (ii).

The above dye mixtures contain, for example, from 5 to 95% by weight,especially from 10 to 90% by weight and preferably from 20 to 80% byweight, of a dye of formula (1a) and/or (1b), based on the total amountof the dyes of formulae (1a), (1b), (1c) and (1d) in the mixture.

Where appropriate, the end product may, in addition, be subjected to aconversion reaction. Such a conversion reaction is, for example, theconversion of the radical Y denoting —CH₂CH₂—U or another reactive groupcapable of conversion to a vinyl moiety into the corresponding vinylform by treatment with dilute sodium hydroxide solution, such as, forexample, the conversion of the β-sulfatoethylsulfonyl orβ-chloroethylsulfonyl group into the vinylsulfonyl radical. Suchreactions are known per se.

The compounds of formulae (13), (14) and (16) are known or can beobtained in a manner known per se.

For example, the compound of formula (16) wherein D₁ is a radical of theabove formula (5) can be prepared by condensation of approximately onemolar equivalent of 2,4,6-trichloro-s-triazine or2,4,6-trifluoro-s-triazine first with approximately one molar equivalentof a compound of formulaT₃-H   (17),at a pH value in the neutral range and at low temperature, for examplefrom 0 to 5° C., and then with approximately one molar equivalent of acompound of formula

at a slightly acidic to neutral pH value, for example pH 4.5-7.5, and ata temperature of, for example, from 0 to 30° C.

Such condensation reactions are known and are described, for example, inEP-A-0 260 227 and U.S. Pat. No. 4,841,049.

Instead of the compound of formula (17), a preliminary product, forexample a diazo component or coupling component, may alternatively beused in the process, the radical T₃ being produced only in the furthercourse of the process by a corresponding diazotisation and couplingreaction.

The reactive dyes according to the invention are either in the form oftheir free acids or, preferably, in the form of salts thereof. Saltsthat come into consideration are, for example, alkali metal, alkalineearth metal and ammonium salts, and salts of an organic amine. Sodium,lithium, potassium and ammonium salts and the salt of the mono-, di- ortri-ethanolamine may be mentioned as examples.

The reactive dyes according to the invention are suitable for dyeing andprinting an extremely wide variety of materials, especiallyhydroxyl-group-containing or nitrogen-containing fibre materials.Examples are paper, silk, leather, wool, polyamide fibres andpolyurethanes and also especially cellulosic fibre materials of allkinds. Such fibre materials are, for example, natural cellulosic fibres,such as cotton, linen and hemp, and also cellulose and regeneratedcellulose. The dyes according to the invention are also suitable fordyeing or printing hydroxyl-group-containing fibres present in blendfabrics, e.g. blends of cotton with polyester fibres or polyamidefibres.

The present invention accordingly relates also to the use of thereactive dyes according to the invention in the dyeing or printing ofhydroxyl-group-containing or nitrogen-containing, especiallycotton-containing, fibre materials.

The reactive dyes according to the invention can be applied to the fibrematerial and fixed to the fibre in a variety of ways, especially in theform of aqueous dye solutions and dye print pastes. They are suitableboth for the exhaust method and for dyeing in accordance with thepad-dyeing method; they can be used at low dyeing temperatures andrequire only short steaming times in the pad-steam process. The degreesof fixing are high and unfixed dye can be washed off easily, thedifference between the degree of exhaust and the degree of fixing beingremarkably small, that is to say the soaping loss being very low. Thereactive dyes according to the invention are also suitable for printing,especially on cotton, but are equally suitable also for printingnitrogen-containing fibres, for example wool or silk or blend fabricsthat contain wool.

The dyeings and prints produced using the reactive dyes according to theinvention have a high tinctorial strength and a high fibre-to-dyebinding stability in both the acidic and the alkaline range, andfurthermore have good fastness to light and very good wet-fastnessproperties, such as fastness to washing, to water, to sea water, tocross-dyeing and to perspiration. The dyeings obtained exhibit fibrelevelness and surface levelness.

The present invention relates furthermore to aqueous inks that comprisea reactive dye of formula (1) wherein Q₁, Q₂, D₁ and D₂ each have thedefinitions and preferred meanings given hereinabove.

The dyes used in the inks should preferably have a low salt content,that is to say they should have a total content of salts of less than0.5% by weight, based on the weight of the dyes. Dyes that haverelatively high salt contents as a result of their preparation and/or asa result of the subsequent addition of diluents can be desalted, forexample, by membrane separation procedures, such as ultrafiltration,reverse osmosis or dialysis.

The inks preferably have a total content of dyes of from 1 to 35% byweight, especially from I to 30% by weight and preferably from 1 to 20%by weight, based on the total weight of the ink. The preferred lowerlimit in this case is a limit of 1.5% by weight, preferably 2% by weightand especially 3% by weight.

The inks may comprise water-miscible organic solvents, for exampleC₁-C₄alcohols, e.g. methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol or iso-butanol; amides, e.g.dimethylformamide or dimethylacetamide; ketones or ketone alcohols, e.g.acetone, diacetone alcohol; ethers, e.g. tetrahydrofuran or dioxane;nitrogen-containing heterocyclic compounds, e.g. N-methyl-2-pyrrolidoneor 1,3-dimethyl-2-imidazolidone, poly-alkylene glycols, e.g.polyethylene glycol or polypropylene glycol; C₂-C₆alkylene glycols andthioglycols, e.g. ethylene glycol, propylene glycol, butylene glycol,triethylene glycol, thio-diglycol, hexylene glycol and diethyleneglycol; other polyols, e.g. glycerol or 1,2,6-hexane-triol; andC₁-C₄alkyl ethers of polyhydric alcohols, e.g. 2-methoxyethanol,2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol,2-[2-(2-methoxyethoxy)ethoxy]ethanol or2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone,diethylene glycol, glycerol or especially 1,2-propylene glycol, usuallyin an amount of from 2 to 30% by weight, especially from 5 to 30% byweight and preferably from 10 to 25% by weight, based on the totalweight of the ink.

In addition, the inks may also comprise solubilisers, e.g.ε-caprolactam.

The inks may comprise thickeners of natural or synthetic origin interalia for the purpose of adjusting the viscosity.

Examples of thickeners that may be mentioned include commerciallyavailable alginate thickeners, starch ethers or locust bean flourethers, especially sodium alginate on its own or in admixture withmodified cellulose, e.g. methyl cellulose, ethyl cellulose,carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethylcellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose,especially with preferably from 20 to 25% by weight carboxymethylcellulose. Synthetic thickeners that may be mentioned are, for example,those based on poly(meth)acrylic acids or poly(meth)acrylamides.

The inks comprise such thickeners, for example, in an amount of from0.01 to 2% by weight, especially from 0.01 to 1% by weight andpreferably from 0.01 to 0.5% by weight, based on the total weight of theink.

The inks may also comprise buffer substances, e.g. borax, borates,phosphates, polyphosphates or citrates. Examples that may be mentionedinclude borax, sodium borate, sodium tetraborate, sodium dihydrogenphosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodiumpentapolyphosphate and sodium citrate. They are used especially inamounts of from 0.1 to 3% by weight, preferably from 0.1 to 1% byweight, based on the total weight of the ink, in order to establish a pHvalue of, for example, from 4 to 9, especially from 5 to 8.5.

As further additives, the inks may comprise surfactants or humectants.

Suitable surfactants include commercially available anionic or non-ionicsurfactants. As humectants in the inks according to the invention therecome into consideration, for example, urea or a mixture of sodiumlactate (advantageously in the form of a 50% to 60% aqueous solution)and glycerol and/or propylene glycol in amounts of preferably from 0.1to 30% by weight, especially from 2 to 30% by weight.

Preference is given to inks having a viscosity of from 1 to 40 mPa·s,especially from 1 to 20 mPa·s and more especially from 1 to 10 mPa·s.

Furthermore, the inks may in addition comprise customary additives, e.g.anti-foams or especially substances that inhibit fungal and/or bacterialgrowth. Such additives are usually used in amounts of from 0.01 to 1% byweight, based on the total weight of the ink.

The inks can be prepared in customary manner by mixing together theindividual constituents in the desired amount of water.

The inks according to the invention are suitable especially for use inrecording systems of a kind in which an ink is forced out of a smallaperture in the form of droplets that are directed onto a substrate onwhich an image is formed. Suitable substrates are, for example, paper,textile fibre materials or plastics films. Suitable recording systemsare, for example commercially available inkjet printers for use in paperor textile printing, or writing instruments, such as fountain pens orballpoint pens, and especially inkjet printers.

Depending on the use, it may be necessary, for example, for theviscosity or other physical properties of the ink, especially propertiesthat have an influence on the affinity for the substrate in question, tobe adapted accordingly.

As examples of paper that can be printed with the inks according to theinvention there may be mentioned commercially available ink-jet paper,photo paper, glossy paper, plastics-coated paper, e.g. Epson Ink-jetPaper, Epson Photo Paper, Epson Glossy Paper, Epson Glossy Film, HPSpecial Ink-jet Paper, Encad Photo Gloss Paper and Ilford Photo Paper.Plastics films that can be printed with the inks according to theinvention are, for example, transparent or cloudy/opaque. Suitableplastics films are, for example, 3M Transparency Film.

As textile fibre materials there come into consideration, for example,nitrogen-containing or hydroxy-group-containing fibre materials, forexample textile fibre materials of cellulose, silk, wool or syntheticpolyamides, preferably cellulose.

The present invention accordingly relates also to a method of printingtextile fibre materials, paper or plastics films, preferably textilefibre materials or paper, and especially textile fibre materials,according to the ink-jet printing method, which comprises using anaqueous ink that comprises a reactive dye of formula (1) wherein Q₁, Q₂,D₁ and D₂ each have the definitions and preferred meanings givenhereinabove.

In the case of the ink-jet printing method, individual droplets of inkare sprayed onto a substrate from a nozzle in a controlled manner. It ismainly the continuous ink-jet method and the drop-on-demand method thatare used for that purpose. In the case of the continuous ink-jet method,the droplets are produced continuously, droplets not required for theprinting operation being discharged into a receptacle and recycled. Inthe case of the drop-on-demand method, on the other hand, droplets aregenerated as desired and used for printing; that is to say, droplets aregenerated only when required for the printing operation. The productionof the droplets can be effected, for example, by means of a piezoink-jet head or by thermal energy (bubble jet). For the processaccording to the invention, printing by means of a piezo ink-jet head ispreferred, but preference is given also to printing according to thecontinuous ink-jet method.

The recordings, for example prints, produced are distinguishedespecially by a high tinctorial strength and a high colour brilliancy aswell as by good light-fastness and wet-fastness properties.

The following Examples serve to illustrate the invention. Unlessotherwise indicated, the temperatures are given in degrees Celsius,parts are parts by weight and percentages relate to % by weight. Partsby weight relate to parts by volume in a ratio of kilograms to litres.

EXAMPLE 1

32.5 parts of an amine of formula D₁₀-NH₂, wherein D₁₀ is a radical offormula

are introduced into 100 parts of water and stirred well. At 10° C.,there are added to the resulting suspension first of all 22.8 parts of a4N sodium nitrite solution and then 41 parts of a 31%naphthalenesulfonic acid solution. Stirring is then carried out for 3hours at from 15 to 20° C.

EXAMPLES 2 to 19

The diazo compounds of the amines indicated in Table 1 can be preparedanalogously to the procedure described in Example 1 by using, instead ofthe amine of formula D₁₀-NH₂ mentioned in Example 1, an equimolar amountof the amines of formula D_(xy)-NH₂ indicated in Table 1.

TABLE 1 Amine Ex. D_(xy)-NH₂ D_(xy) 2 D₁₁-NH₂

3 D₁₂-NH₂

4 D₁₃-NH₂

5 D₁₄-NH₂

6 D₁₅-NH₂

7 D₁₆-NH₂

8 D₁₇-NH₂

9 D₁₈-NH₂

10 D₁₉-NH₂

11 D₂₀-NH₂

12 D₂₁-NH₂

13 D₂₂-NH₂

14 D₂₃-NH₂

15 D₂₄-NH₂

16 D₂₅-NH₂

17 D₂₆-NH₂

18 D₂₇-NH₂

19 D₂₈-NH₂

EXAMPLE 20

a) 36.9 parts of cyanuric chloride are stirred in 150 parts of ice/waterand a small amount of wetting agent. At from 0 to 2° C., a solution of25.25 parts of taurine in 50 parts of water is introduced in the courseof 40 minutes and condensation is carried out at a pH of from 7 to 8 bythe dropwise addition of 2N sodium hydroxide solution. Stirring is thencarried out at from 0 to 5° C. and a pH of from 7 to 7.5 until cyanuricchloride can no longer be detected. A neutral solution of 39.48 parts of1,3-phenylenediamine-4-sulfonic acid in 100 parts of water is thenadded. Condensation is carried out at a temperature of from 5 to 20° C.and the pH is maintained at from 8 to 9 by the addition of 2N sodiumhydroxide solution. When condensation is complete, the reaction solutionis salted out using KCl, filtered and washed with concentrated KClsolution. After drying, the intermediate of formula

is obtained.

b) 68 parts of the compound according to a) are suspended in 300 partsof water. The diazotized amine from Example 3, which is preparedaccording to Example 1 from 45 parts of the amine of formula D₁₂-NH₂, isthen added in the course of 10 minutes at from 0 to 5° C., and the pH ismaintained at from 6 to 8.5 using soda solution (20%). When coupling iscomplete, the yellow dye is precipitated using KCl, and the suspensionobtained is filtered and dried in vacuo, yielding the monoazo compoundof formula

c) 83 parts of the compound according to Example b) are dissolved in 700parts of water and diazotized according to the customary method withsodium nitrite and HCl at from 0 to 5° C.

EXAMPLE 21

A solution of 21.5 parts of 2-amino-5-naphthol-7-sulfonic acid in 250parts of water (pH 7) is added dropwise at from 0 to 5° C. to the acidsuspension of the diazo compound of the amine of formula D₁₀-NH₂obtained according to Example 1. The mixture is then heated to roomtemperature and stirred for approximately 5 h until coupling is complete(first coupling). The reaction mixture is then cooled to from 5 to 10°C., the pH value is increased to approximately 4.5 using an aqueoussodium hydrogen carbonate solution, and the suspension of the diazocompound obtained according to Example 20c) is slowly added dropwise,the pH value being maintained during the dropwise addition atapproximately 4.5 by the addition of an aqueous sodium hydrogencarbonate solution and the temperature being maintained at approximately5° C. After the dropwise addition, the pH value is adjusted to 6 (secondcoupling). When coupling is complete, the dye solution is freed of saltby dialysis and concentrated by evaporation in vacuo. A compound isobtained which in the form of the free acid corresponds to formula

(λ_(max): 550 nm), which dyes wool and cellulose in a bluish violetshade having good allround fastness properties.

EXAMPLES 22 TO 39v

A compound of the general formula

can be prepared analogously to the procedure described in Example 21 byusing, instead of the amine of formula (101), an equimolar amount of oneof the amines of formula D_(xy)-NH₂ indicated in Table 2. The dyes dyewool and celluose in orange to blue shades having good allround fastnessproperties.

TABLE 2 Amine λ_(max) Ex. D_(xy)-NH₂ D_(xy) [nm] 22 D₂₉-NH₂

550 23 D₃₀-NH₂

536 24 D₃₁-NH₂

570 25 D₃₂-NH₂

583 26 D₃₃-NH₂

572 27 D₃₄-NH₂

570 28 D₃₅-NH₂

536 29 D₃₆-NH₂

570 30 D₃₇-NH₂

574 31 D₃₈-NH₂

535 32 D₃₉-NH₂

541 33 D₄₀-NH₂

540 34 D₄₁-NH₂

543 35 D₄₂-NH₂

538 36 D_(43a)-NH₂ − D_(43g)-NH₂

T₃: 36a D_(43a)-NH₂ D_(43a)

501 36b D_(43b)-NH₂ D_(43b)

488 36c D_(43c)-NH₂ D_(43c)

486 36d D_(43d)-NH₂ D_(43d)

505 36e D_(43e)-NH₂ D_(43e)

516 36f D_(43f)-NH₂ D_(43f)

520 36g D_(43g)-NH₂ D_(43g)

520 37 D_(44a)-NH₂ − D_(44g)-NH₂

T₃: 37a D_(44a)-NH₂ D_(44a)

495 37b D_(44b)-NH₂ D_(44b)

489 37c D_(44c)-NH₂ D_(44c)

487 37d D_(44d)-NH₂ D_(44d)

497 37e D_(44e)-NH₂ D_(44e)

514 37f D_(44f)-NH₂ D_(44f)

513 37g D_(44g)-NH₂ D_(44g)

514 38 D_(45a)-NH₂ − D_(45v)-NH₂

39 D_(46a)-NH₂ − D_(46v)-NH₂

D: 38a/39a D_(45a/46a)-NH₂ D_(45a/46a)

516 (39a)/ 497 (40a) 38b/39b D_(45b/46b)-NH₂ D_(45b/46b)

493 (40b) 38c/39c D_(45c/46c)-NH₂ D_(45c/46c)

503 (40c) 38d/39d D_(45d/46d)-NH₂ D_(45d/46d)

518 (39d) 38e/39e D_(45e/46e)-NH₂ D_(45e/46e)

510 (39e) 38f/39f D_(45f/46f)-NH₂ D_(45f/46f)

524 (39f) 38g/39g D_(45g/46g)-NH₂ D_(45g/46g)

520 (39g) 38h/39h D_(45h/46h)-NH₂ D_(45h/46h)

518 (39h) 38i/39i D_(45i/46i)-NH₂ D_(45i/46i)

520 (39i) 38j/39j D_(45j/46j)-NH₂ D_(45j/46j)

528 (39j) 38k/39k D_(45k/46k)-NH₂ D_(45k/46k)

518 (39k) 38l/39l D_(45l/46l)-NH₂ D_(45l/46l)

522 (39l) 38m/39m D_(45m/46m)-NH₂ D_(45m/46m)

520 (39m) 38n/39n D_(45n/46n)-NH₂ D_(45n/46n)

510 (39n) 38o/39o D_(45o/46o)-NH₂ D_(45o/46o)

508 (39o) 38p/39p D_(45p/46p)-NH₂ D_(45p/46p)

512 (39p) 38q/39q D_(45q/46q)-NH₂ D_(45q/46q)

525 (39q) 38r/39r D_(45r/46r)-NH₂ D_(45r/46r)

520 (39r) 38s/39s D_(45s/46s)-NH₂ D_(45s/46s)

519 (39s) 38t/39t D_(45t/46t)-NH₂ D_(45t/46t)

508 (39t) 38u/39u D_(45u/46u)-NH₂ D_(45u/46u)

525 (39u) 38v/39v D_(45v/46v)-NH₂ D_(45v/46v)

514 (39v)

EXAMPLES 40 TO 57

By proceeding as described in Example 21 but, instead of using the acidsuspension of the diazo compound of the amine of formula D₁₀-NH₂, usingan equimolar amount of the diazo compound of an amine of formulaD_(xy)-NH₂, a dye of formula

is obtained wherein D_(xy) corresponds to one of the radicals listed inTable 3, the definitions given in Table 1 applying to that radical. Thedyes dye wool and cellulose in bluish violet shades having good allroundfastness properties.

TABLE 3 Ex. D_(xy) 40 D₁₁ 41 D₁₂ 42 D₁₃ 43 D₁₄ 44 D₁₅ 45 D₁₆ 46 D₁₇ 47D₁₈ 48 D₁₉ 49 D₂₀ 50 D₂₁ 51 D₂₂ 52 D₂₃ 53 D₂₄ 54 D₂₅ 55 D₂₆ 56 D₂₇ 57D₂₈

EXAMPLES 58 TO 62

The compounds of the following formulae can be prepared analogously tothe procedure described in Example 21

which dye wool and cellulose in violet to dark-blue shades having goodallround fastness properties.

Dyeing Procedure I

100 parts of cotton fabric are introduced at 60° C. into 1500 parts of adye bath containing 45 g/l of sodium chloride and 2 parts of thereactive dye obtained according to Example 21. After 45 minutes at 60°C., 20 g/l of calcined soda are added. Dyeing is continued for a further45 minutes at that temperature. The dyed goods are then rinsed, soapedat the boil for a quarter of an hour with a non-ionic detergent, rinsedagain and dried.

As an alternative to the above procedure, the dyeing can be carried outat 80° C. instead of at 60° C.

Dyeing Procedure II

0.1 part of the dye according to Example 21 is dissolved in 200 parts ofwater, and 0.5 part of sodium sulfate, 0.1 part of a levelling agent(based on the condensation product of a higher aliphatic amine andethylene oxide) and also 0.5 part of sodium acetate are added. The pH isthen adjusted to a value of 5.5 using acetic acid (80%). The dye bath isheated at 50° C. for 10 minutes and then 10 parts of a woollen fabricare added. Heating is then carried out in the course of approximately 50minutes to a temperature of 100° C. and dyeing is carried out at thattemperature for 60 minutes, after which the dye bath is allowed to cooland the dyed goods are removed. The woollen fabric is washed with hotand cold water, and is then spun and dried.

Printing Procedure I

3 parts of the dye obtained according to Example 21 are sprinkled, withrapid stirring, into 100 parts of a stock thickener containing 50 partsof 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea,1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodiumhydrogen carbonate. The print paste so obtained is used to print acotton fabric, and the resulting printed material is dried and steamedin saturated steam for 2 minutes at 102° C. The printed fabric is thenrinsed, if desired soaped at the boil and rinsed again, and subsequentlydried.

Printing Procedure II

(a) Mercerised cotton satin is pad-dyed with a liquor containing 30 g/lof sodium carbonate and 50 g/l of urea (70% liquor pick-up) and dried.

(b) Using a drop-on-demand inkjet head (bubble jet), the cotton satinpretreated according to Step (a) is printed with an aqueous inkcontaining

-   -   10% by weight of the reactive dye according to Example 21,    -   20% by weight of 1,2-propylene glycol and    -   70% by weight of water.

The print is dried completely and fixed in saturated steam for 8 minutesat 102° C., cold-rinsed, washed off at the boil, rinsed again and dried.

1. A reactive dye of formula

wherein Q₁ and Q₂ are each independently of the other hydrogen or unsubstituted or substituted C₁-C₄ alkyl, D₁ corresponds to a radical of formula (5) or (11)

wherein R₅ is hydrogen or C₁-C₄ alkyl, (R₇)₀₋₃ denotes from 0 to 3 identical or different substituents selected from the group halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ alkanoylamino, carboxy and sulfo, X₄ is fluorine or chlorine, Z₂ is a fibre-reactive radical of formula —SO₂—Y   (3a), wherein Y is vinyl or β-sulfatoethyl, T₃ is a radical of formula

wherein (R₇)₀₋₃ is as defined hereinabove, (R₈)₀₋₃ denotes from 0 to 3 identical or different substituents from the group halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁-C₄ alkyl, C₁-C₄ alkoxy unsubstituted or substituted by hydroxy, sulfato or by C₁-C₄ alkoxy, amino, C₂-C₄ alkanoylamino, ureido, hydroxy, carboxy, sulfomethyl, C₁-C₄ alkylsulfonylamino and sulfo, R₁₁ and R₁₃ are each independently of the other hydrogen, C₁-C₄ alkyl or phenyl, R₁₂ is hydrogen, cyano, carbamoyl or sulfomethyl, (R₁₄)₀₋₃ denotes from 0 to 3 identical or different substituents from the group C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, carboxy and sulfo, and Z₂ is as defined hereinabove, K₃ is the radical of a coupling component of formula

wherein R′₈ is hydrogen, sulfo, or C₁-C₄ alkoxy unsubstituted or substituted in the alkyl moiety by hydroxy or by sulfato, and R′_(8a) is hydrogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ alkanoylamino, ureido or a radical of formula

wherein R_(1a) is hydrogen, T₁ is amino; N-mono- or N,N-di-C₁-C₄ alkylamino unsubstituted or substituted in the alkyl moiety/moieties by hydroxy, sulfato or by sulfo; morpholino; phenylamino unsubstituted or substituted on the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or by methoxy; or N—C₁-C₄ alkyl-N-phenylamino unsubstituted or substituted in the same way on the phenyl ring and in which the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato; or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups, and X₁ is chlorine D₂ has the same definition as D₁ or is a radical of formula

wherein (Q₃)₀₋₃ denotes from 0 to 3 identical or different substituents selected from the group halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, carboxy and sulfo and Z₁ is a radical of formula —SO₂—Y   (3a), —NH—CO—(CH₂)_(m)—SO₂—Y  (3b), —CONH—(CH₂)_(n)—SO₂—Y   (3c), —NH—CO—CH(Hal)-CH₂-Hal   (3d) or —NH—CO—C(Hal)=CH₂   (3e), Y is vinyl or a —CH₂—CH₂—U radical and U is a group that is removable under alkaline conditions, m and n are each independently of the other the number 2, 3 or 4, and Hal is halogen, with the proviso that the dye of formula (1) does not contain a hydroxysulfonylmethyl group.
 2. A reactive dye according to claim 1, wherein Q₁ and Q₂ are hydrogen.
 3. A reactive dye according to claim 1, wherein U is —Cl —Br, —F, —OSO₃H, —SSO₃H, —OCC—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄ alkyl or —OSO₂—N(C₁-C₄ alkyl)₂.
 4. A reactive dye according to claim 1 wherein D₂ is a radical of formula

wherein Y is vinyl or β-sulfatoethyl.
 5. A process for the preparation of a dye of formula (1) according to claim 1, which comprises (i) diazotisation of approximately one molar equivalent of an amine of formula D₂-NH₂  (13) and reaction with approximately one molar equivalent of a compound of formula

to form a compound of formula

and (ii) diazotisation of approximately one molar equivalent of an amine of formula D₁-NH₂  (16) and reaction with approximately one molar equivalent of the compound of formula (15a) obtained according to (i) to form a compound of formula (1) according to claim 1 wherein D₁, D₂, Q₁ and Q₂ each have the definitions given in claim
 1. 6. An aqueous ink that comprises a reactive dye of formula (1) according to claim
 1. 7. A process for printing a substrate comprising spraying individual droplets of an aqueous ink onto the substrate from a nozzle in a controlled manner wherein the aqueous ink comprises a reactive dye of formula

wherein Q₁ and Q₂ are each independently of the other hydrogen or unsubstituted or substituted C₁-C₄alkyl, D₁ corresponds to a radical of formula (5) or (11)

wherein R₅ is hydrogen or C₁-C₄ alkyl, (R₇)₀₋₃ denotes from 0 to 3 identical or different substituents selected from the group halogen, C₁-₄alkyl, C₁-C₄ alkoxy, C₂-C₄ alkanoylamino, carboxy and sulfo, X₄ is fluorine or chlorine, Z₂ is a fibre-reactive radical of formula —SO₂—Y  (3a), wherein Y is vinyl or β-sulfatoethyl, T₃ is a radical of formula

wherein (R₇)₀₋₃ is as defined hereinabove, (R₈)₀₋₃ denotes from 0 to 3 identical or different substituents from the group halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁-C₄ alkyl, C₁-C₄ alkoxy unsubstituted or substituted by hydroxy, sulfato or by C₁-C₄ alkoxy, amino, C₂-C₄ alkanoylamino, ureido, hydroxy, carboxy, sulfomethyl, C₁-C₄ alkylsulfonylamino and sulfo, R₁₁ and R₁₃ are each independently of the other hydrogen, C₁-C₄ alkyl or phenyl, R₁₂ is hydrogen, cyano, carbamoyl or sulfomethyl, (R₁₄)₀₋₃ denotes from 0 to 3 identical or different substituents from the group C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, carboxy and sulfo, and Z₂ is as defined hereinabove, K₃ is the radical of a coupling component of formula

wherein R′₈ is hydrogen, sulfo, or C₁-C₄ alkoxy unsubstituted or substituted in the alkyl moiety by hydroxy or by sulfato, and R′_(8a) is hydrogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ alkanoylamino, ureido or a radical of formula

wherein R_(1a) is hydrogen, T₁ is amino; N-mono- or N,N-di-C₁-C₄ alkylamino unsubstituted or substituted in the alkyl moiety/moieties by hydroxy, sulfato or by sulfo; morpholino; phenylamino unsubstituted or substituted on the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or by methoxy; or N—C₁-C₄ alkyl-N-phenylamino unsubstituted or substituted in the same way on the phenyl ring and in which the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato; or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups, and X₁ is chlorine D₂ has the same definition as D₁ or is a radical of formula

wherein (Q₃)₀₋₃ denotes from 0 to 3 identical or different substituents selected from the group halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxy and sulfo and Z₁ is a radical of formula —SO₂—Y  (3a), —NH—CO—(CH₂)_(m)—SO₂—Y  (3b), —CONH—(CH₂)_(n)—SO₂—Y  (3c), —NH—CO—CH(Hal)-CH₂-Hal  (3d) or —NH—CO—C(Hal)=CH₂  (3e), Y is vinyl or a —CH₂—CH₂—U radical and U is a group that is removable under alkaline conditions, m and n are each independently of the other the number 2, 3 or 4, and Hal is halogen with the proviso that the dye of formula (1) does not contain a hydroxysulfonylmethyl group.
 8. The process of claim 7 wherein the substrate is selected from textile fibre material, paper and plastic film.
 9. A method for dyeing fibre material which comprises applying a reactive dye of formula (1) according to claim 1 to the fibre material and fixing the reactive dye to the fibre material.
 10. The method according to claim 9 wherein the fibre material is a hydroxyl-group-containing fibre material or a nitrogen-group-containing fibre material.
 11. The method of claim 9 wherein the fibre material is a cellulosic fibre material.
 12. The method of claim 11 wherein the cellulosic fibre material is a cotton-containing fibre material. 